活性5-O黃酮苷的合成及新型糖苷化方法的研究
發(fā)布時間：2018-10-23 20:04
【摘要】：一、金催化糖苷化立體選擇性構(gòu)建黃酮類5-O糖苷鍵山茶苷B(camellianins B)是含黃酮類5-O-糖苷鍵化合物典型的代表,具有較好的降血糖活性;野茶樹(Camellia sinensis)和灌木粗榧(Cephalotaxus sinensis)均含有山茶苷B。我們利用鄰炔基苯甲酸酯給體在Au(I)促進(jìn)下高效的完成了芹菜素5-O糖苷鍵的構(gòu)建。首次經(jīng)過三條不同的合成路線完成了山茶苷B,第一條為線性式的合成,另外兩條均是匯聚式的合成。三條合成路線的最終產(chǎn)物均是同一個化合物,有力的證明了合成的正確性。我們經(jīng)過全Ac保護(hù)商品山茶苷B,分析了1H NMR的一維譜和二維譜修正了山茶苷A和山茶苷B之前報道的結(jié)構(gòu)。二、新型高效的糖苷化方法研究寡糖類化合物和糖綴合物在生命過程中扮演著非常重要的角色,通過糖苷化方法構(gòu)建糖苷鍵是合成寡糖和糖綴合物的關(guān)鍵。本文介紹了一種新型的以鄰炔基酚醚(MPEP)為離去基的高效糖苷化方法,該方法具有底物普適性好,反應(yīng)條件溫和,給體穩(wěn)定且易于制備,反應(yīng)高效等優(yōu)點。同時以鄰炔基酚醚(MPEP)為給體成功應(yīng)用于“潛在-活化”糖苷化策略高效的完成了具有生物活性的肺炎雙球菌三糖糖苷鍵的構(gòu)建。之后我們將鄰炔基酚醚給體與Schmidt給體以及炔酯給體進(jìn)行正交性的一鍋法合成研究,并分別在七小時內(nèi)以68%和65%的總收率完兩個四糖的合成研究。
[Abstract]:One is that gold catalyzes the stereoselectivity of glycosylation to construct flavonoid 5-O-glycoside B (camellianins B), which is a typical representative of flavonoid 5-Oglucoside bond compounds, and has good hypoglycemic activity, and both (Camellia sinensis) and (Cephalotaxus sinensis) contain camellia glucoside B. We successfully constructed the apigenin 5-O glycoside bond by using o-acetylbenzoate donor under the promotion of Au (I). Camelopin B was synthesized by three different synthetic routes for the first time. The first one was linear synthesis and the other two were convergent synthesis. The final product of the three synthetic routes is the same compound, which can prove the correctness of the synthesis. The one-dimensional and two-dimensional spectra of 1H NMR were analyzed and the previously reported structures of camoside A and camelopside B were modified by using the whole Ac protected commercial camelloside B. Secondly, a new and efficient method of glycoside reaction is used to study oligosaccharide compounds and glycoconjugates, which play a very important role in the life process. The key to the synthesis of oligosaccharides and glycoconjugates is to construct glycoside bonds by the method of glycoside glycosylation. In this paper, a new method of glycosylation with o-acetylphenol ether (MPEP) as departure group is introduced. The method has the advantages of good substrate universality, mild reaction conditions, stable donor, easy preparation and high reaction efficiency. At the same time, using o-acetylphenol ether (MPEP) as donor, it was successfully applied to the "potential-activated" glycosylation strategy to construct the biologically active triglycosylated glycoside bond of Diplococcus pneumoniae. After that, the orthoacetylphenol ether donor, Schmidt donor and alkynyl ester donor were synthesized by one-pot method, and the synthesis of two tetraccharides was completed in 68% and 65% overall yield within seven hours, respectively.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O629.13
本文編號：2290328
[Abstract]:One is that gold catalyzes the stereoselectivity of glycosylation to construct flavonoid 5-O-glycoside B (camellianins B), which is a typical representative of flavonoid 5-Oglucoside bond compounds, and has good hypoglycemic activity, and both (Camellia sinensis) and (Cephalotaxus sinensis) contain camellia glucoside B. We successfully constructed the apigenin 5-O glycoside bond by using o-acetylbenzoate donor under the promotion of Au (I). Camelopin B was synthesized by three different synthetic routes for the first time. The first one was linear synthesis and the other two were convergent synthesis. The final product of the three synthetic routes is the same compound, which can prove the correctness of the synthesis. The one-dimensional and two-dimensional spectra of 1H NMR were analyzed and the previously reported structures of camoside A and camelopside B were modified by using the whole Ac protected commercial camelloside B. Secondly, a new and efficient method of glycoside reaction is used to study oligosaccharide compounds and glycoconjugates, which play a very important role in the life process. The key to the synthesis of oligosaccharides and glycoconjugates is to construct glycoside bonds by the method of glycoside glycosylation. In this paper, a new method of glycosylation with o-acetylphenol ether (MPEP) as departure group is introduced. The method has the advantages of good substrate universality, mild reaction conditions, stable donor, easy preparation and high reaction efficiency. At the same time, using o-acetylphenol ether (MPEP) as donor, it was successfully applied to the "potential-activated" glycosylation strategy to construct the biologically active triglycosylated glycoside bond of Diplococcus pneumoniae. After that, the orthoacetylphenol ether donor, Schmidt donor and alkynyl ester donor were synthesized by one-pot method, and the synthesis of two tetraccharides was completed in 68% and 65% overall yield within seven hours, respectively.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O629.13
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 魏榮寶;張大為;梁婭;盧俊瑞;李紅姬;;有機化學(xué)中的異頭效應(yīng)[J];有機化學(xué);2008年10期
，本文編號：2290328
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